Shaped detergent product comprising aminopolycarboxylate

ABSTRACT

A shaped detergent product comprising 10 to 100 wt. % of a first solid phase and 0 to 90 wt. % of one or more other phases, wherein the first solid phase comprises: a) non-crystalline chiral aminopolycarboxylate; b) non-crystalline organic acid other than component a); c) at most 30 wt. % water; d) at most 50 wt. % of non-crystalline water-soluble component other than component a) or component b); e) at most 20 wt. % of homogeneously dispersed crystalline material; wherein the combination of the components a), b) and c) is present in the first solid phase in a concentration of at least 35 wt. % of the total weight of the solid phase; and wherein components a), b) and c) are present in the solid phase in a ratio of from 25 to 88 parts by weight of free acid equivalent of component a): from 10 to 60 parts by weight of free acid equivalent of component b): from 2 to 30 parts by weight of component c); and wherein the shaped detergent product comprises at least 0.5 wt. % surfactant.

FIELD OF THE INVENTION

The present invention relates to a shaped detergent product.Particularly, the present invention relates to a shaped detergentproduct comprising a first solid phase which comprises non-crystallinechiral aminopolycarboxylate, non-crystalline organic acid not being anaminopolycarboxylate and water.

BACKGROUND OF THE INVENTION

Detergent products typically contain several different activecomponents, including builders, surfactants, enzymes and bleachingagents. Surfactants are employed to remove stains and soil and todisperse the released components into the cleaning liquid. Enzymes helpto remove stubborn stains of proteins, starch and lipids by hydrolyzingthese components. Bleach is used to remove stains by oxidizing thecomponents that make up these stains. In order to reduce the negativeeffects of in particular calcium and magnesium ions on stain/soilremoval so called ‘builders’ (complexing agents) are commonly applied indetergent products.

Shaped detergent products are known in the art. Detergent tablets are anexample of a shaped detergent product. Tablets typically comprise amixture of components that are solid at room temperature and componentsthat are liquid at room temperature. The solid components are usuallypresent in granular form for ease of processing and speed ofdissolution/dispersion. The tablets are normally prepared by admixtureof the tablet components followed by compaction to a shaped body.

Shaped detergent products in the form of multi-phase tablets are alsoknown in the art. These multi-phase tablets contain one or morecomponent formulations commonly present in a layered arrangement/bodywith insert formation. The component formulations contained inmulti-phase tablets are usually composed of opaque, compressedmaterials.

Phosphorous based builders have been used for many years in a widevariety of detergent products. Some of the phosphorus based builders,such as trisodium phosphate and sodium tripolyphospate (STPP), have seta benchmark in the dishwasher detergent industry as having excellentperformance. As such, phosphorus-containing builder components aregenerally considered to be “high-performance” builders. The use ofphosphorous based builders in detergent products has led toenvironmental problems such as eutrophication. To curtail such problemsmany jurisdictions have, or are in the process of, issuing laws andregulations to restrict the maximum amount of phosphorous in detergentproducts. As such there has been a need for more environmentallyfriendly alternative builders, which have on-par effectiveness and whichare also cost-effective. Examples of such alternative builders areaminopolycarboxylates, such as glutamic acid N,N-diacetic acid (GLDA),methylglycinediacetic acid (MGDA) and ethylenediaminetetraacetic acid(EDTA). A drawback of many of such aminopolycarboxylates is that theytend to be hygroscopic.

WO 2014/086662 discloses a solid GLDA (i.e. a aminopolycarboxylate)material comprising a combination of GLDA, sulphuric acid and sodiumsulfate crystals. Also described is a process of producing a solid GLDAcomposition comprising the consecutive steps of:

-   -   combining a GLDA sodium salt and sulfuric acid in a high water        activity phase; and    -   allowing water to evaporate from said phase to produce a        precipitate.

It would be desirable to have available shaped detergent productscomprising solid aminopolycarboxylate that provide one or more importantproduct benefits, such as attractive appearance, improved stability andimproved dissolution/dispersion properties.

It is an object of the present invention to provide a shaped detergentproduct containing aminopolycarboxylate that provides such benefits.

SUMMARY OF THE INVENTION

One or more of the above objectives is achieved, in a first aspect ofthe invention, by shaped detergent product comprising 10 to 100 wt. % ofa first solid phase and 0 to 90 wt. % of one or more other phases, saidfirst solid phase comprising:

-   -   a) non-crystalline chiral aminopolycarboxylate;    -   b) non-crystalline organic acid other than component a);    -   c) at most 30 wt. % water;    -   d) at most 50 wt. % of non-crystalline water-soluble component        other than component a) or component b);    -   e) at most 20 wt. % of homogeneously dispersed crystalline        material;    -   wherein the combination of the components a), b) and c) is        present in the first solid phase in a concentration of at least        35 wt. % of the total weight of said solid phase; and    -   wherein components a), b) and c) are present in the solid phase        in a ratio of from 25 to 88 parts by weight of free acid        equivalent of component a): from 10 to 60 parts by weight of        free acid equivalent of component b): from 2 to 30 parts by        weight of component c); and    -   wherein the shaped detergent product comprises at least 0.5 wt.        % surfactant.

It was unexpectedly discovered that it is possible to prepare a shapeddetergent product containing an attractive translucent or eventransparent solid phase that comprises aminopolycarboxylate, organicacid water in above mentioned weight ratios. Very attractive shapeddetergent products can be produced by incorporating such atranslucent/transparent and even glossy solid phase as a visibleelement.

The aforementioned solid phase can also suitably be applied as anexternal, optionally transparent, coating of the shaped detergentproduct.

It was found that a translucent/transparent solid phase according to thepresent invention can be produced if it contains not more than 50 wt. %of other non-crystalline water-soluble component and not more than 20wt. % homogeneously dispersed crystalline material.

It was unexpectedly discovered that a translucent/transparent solidphase according to the present invention can be prepared from an aqueoussolution containing aminopolycarboxylate, acid and at least 35 wt. %water by reducing the water content of the solution to 30 wt. % or lessto produce a liquid desiccated mixture whilst keeping the liquid mixtureat a temperature of at least 50 degrees Celsius, followed by cooling ofthe desiccated mixture to a temperature of less than 25 degrees Celsiusto obtain the first solid phase.

Although the inventors do not wish to be bound by theory, it is believedthat the desiccated liquid that is formed by reducing the water contentof the solution to 30 wt. % or less is a substantially amorphousmaterial in its viscous (or rubbery) state. By cooling the desiccatedliquid, the viscosity increases to a level where the material becomessolid. This process offers the advantage that it allows for theproduction of the first solid phase in the form of (shaped) pieces.Furthermore, the process can be used to coat a solid substrate with thefirst solid phase by coating the substrate with the hot liquiddesiccated mixture and allowing the hot mixture to cool down.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 : photograph of the solid amorphous phase of Example 1.

FIG. 2 : photograph of the solid amorphous phase of Example 2.

FIG. 3 : photograph of the solid amorphous phase of Example 3.

FIG. 4 : a WAXS graph of Example 1 (according to the disclosure): thepresence of crystals is not detected.

DETAILED DESCRIPTION Definitions

Weight percentage (wt. %) is based on the total weight of the shapeddetergent product or of the first solid phase as indicated, unlessotherwise stated. It will be appreciated that the total weight amount ofingredients will not exceed 100 wt. %. Whenever an amount orconcentration of a component is quantified herein, unless indicatedotherwise, the quantified amount or quantified concentration relates tosaid component per se, even though it may be common practice to add sucha component in the form of a solution or of a blend with one or moreother ingredients. It is furthermore to be understood that the verb “tocomprise” and its conjugations is used in its non-limiting sense to meanthat items following the word are included, but items not specificallymentioned are not excluded. Finally, reference to an element by theindefinite article “a” or “an” does not exclude the possibility thatmore than one of the elements is present, unless the context clearlyrequires that there be one and only one of the elements. The indefinitearticle “a” or “an” thus usually means “at least one”. Unless otherwisespecified all measurements are taken at standard conditions. Whenever aparameter, such as a concentration or a ratio, is said to be less than acertain upper limit it should be understood that in the absence of aspecified lower limit the lower limit for said parameter is 0.

The term ‘distinctive’ or ‘distinct’ as used herein in relation to thefirst solid phase means that this phase is visuallydistinct/distinguishable by the untrained human eye.

The term ‘solid’ according to the invention is according to itscommonplace usage. For example, a wineglass is considered a solid incommon place usage although in a strict physical sense it is anextremely viscous liquid.

The term ‘aminopolycarboxylate’ includes its partial and full acidsunless otherwise specified. The salts, rather than the full acids, ofthe aminopolycarboxylates are more preferred, and particularly preferredare the alkali salts thereof.

The term ‘acid’ includes partial or full alkali salts thereof unlessotherwise specified.

Concentrations expressed in wt. % of ‘free acid equivalent’ refer to theconcentration of an aminopolycarboxylate or an acid expressed as wt. %,assuming that the aminopolycarboxylate of acid is exclusively present infully protonated from. The following table shows how the free acidequivalent concentrations can be calculated for some (anhydrous)aminopolycarboxylates and (anhydrous) acid salts.

Wt. % Conversion Wt. % free acid salt factor equivalent GLDA(tetrasodium salt) 50 263.1/351.1 37.5 MGDA (trisodium salt) 50205.1/271.1 37.8 Citric acid (monosodium 50 192.1/214.1 44.9 salt)Sodium acetate 50 60.0/82.0 36.6

The term ‘translucency’ as used herein refers to the ability of light inthe visible spectrum to pass through the first solid phase, at least inpart. To quantify, preferably it is evaluated based on a path-length of0.5 cm through the first solid phase, measuring the amount of lightpassing through. The first solid phase of the shaped detergent productis deemed to be translucent if under the aforementioned measurementconditions within the wavelength range of 400 to 700 nm it has a maximumTransmittance of at least 5%. The first solid phase is deemed to betransparent if within the aforementioned wavelength range it has amaximum Transmittance of at least 20%. Here the Transmittance is definedas the ratio between the light intensity measured after the light haspassed through the sample of first solid phase and the light intensitymeasured when the sample has been removed.

Gloss is the fraction of light that is reflected in a specular(mirror-like) direction. The angle of the incident light at which glossis measured is 20 degrees to obtain a measurement for ‘high glossfinish’, 60 degrees for ‘mid gloss finish’ and 85 degrees for ‘mattfinish’. Good gloss attributes provides better visual appeal and cue'sglass cleaning performance of the solid composition. These gloss valuesare measured using a Rhopoint IQ (Goniophotometer; Supplier RhopointInstruments) according to supplier instructions. To measure glossinessof the solid composition, this is done on an (isolated, continuous)sample of the solid composition, having a thickness of 0.5 cm, a flatsmooth surface (e.g. shaped like a disk or plate) and using white paperas background (100% recycled paper, bright white; Supplier: OfficeDepot).

Advantageously, the first solid phase has the following gloss propertiesto provide even better visual appeal:

-   -   A specular reflectance at 20 degrees of incident light of at        least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% and        even more preferably at least 60%. Preferably the reflectance at        20 degrees of at most 95%, 90%, 85%, 80% and more preferably at        most 75%. The most advantageous reflectance at 20 degrees being        from 40 to 85%, more preferably from 50 to 80% and even more        preferably from 55 to 75%.    -   A specular reflectance at 60 degrees of incident light of at        least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%,        65%, 70%, 75%, 80%, 85%. Preferably the reflectance at 60        degrees of at most 99.5%, 99.0%, 98.5% and more preferably        98.0%. The most advantageous reflectance at 60 degrees being        from 50 to 99.5%, more preferably from 70 to 99.0% and even more        preferably from 80 to 98.5%.    -   A specular reflectance at 85 degrees of incident light of at        least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% and        even more preferably at least 60%. Preferably the reflectance at        85 degrees of at most 95%, 90%, 85%, 80% and more preferably at        most 75%. The most advantageous reflectance at 85 degrees being        from 40 to 85%, more preferably from 50 to 80% and even more        preferably from 55 to 75%.

Of course even more advantageously the first solid phase has thepreferred reflectance at 20, 60 and 85 degrees in combination (i.e. hasa good high gloss finish and a good mid gloss finish and a good mattfinish).

The first solid phase may contain a quantity of homogeneously dispersedcrystalline material. The first solid phase can be translucent even inthe presence of such homogenously dispersed crystalline material andprovide a desirable ‘milky glass’ like appearance. Preferably,homogeneously dispersed crystalline material, if present, is present insuch quantities that the first solid phase has a maximum Transmittancein the wavelength range of 400 to 700 nm of at least 2%, more preferablyof at least 5%.

In one preferred embodiment the amount of homogenously dispersedcrystalline material other than component a) or component b) in thefirst solid phase preferably is from 0.1 to 15 wt. %, more preferably0.2 to 10 wt. %, even more preferably 0.5 to 5 wt. % and still even morepreferably from 0.7 to 3 wt. %, based on the weight of the first solidphase. The crystalline material can be any suitable crystallinematerial, but preferably is detergent active crystalline material. Inanother preferred embodiment the first solid phase does not containcrystalline material, i.e. in accordance with this embodiment, the firstsolid phase is essentially amorphous.

The first solid phase of the shaped detergent of the invention comprisesthe combination of component a), component b) and component c) in aconcentration of at least 35 wt. % of the total weight of said solidphase. Preferably, the combination of a) to c) constitutes at least 40wt. %, more preferably at least 50 wt. %, even more preferably at least55 wt. % of the first solid phase.

Preferably, components a), b) and c) are present in the first solidphase in a ratio of from 35 to 80 parts by weight of free acidequivalent of component a): from 15 to 50 parts by weight of free acidequivalent of component b): from 5 to 25 parts by weight of componentc). More preferably, components a), b) and c) are present in the solidphase in a ratio of from 30 to 70 parts by weight of free acidequivalent of component a): from 20 to 50 parts by weight of free acidequivalent of component b): from 6 to 20 parts by weight of componentc).

According to another preferred embodiment, the combination of componentsa), b), c) and e) is present in the first solid phase in a combinedconcentration of at least 80 wt. %, more preferably of at least 90 wt. %of the total weight of said solid phase.

Non-Crystalline Chiral Aminopolycarboxylate

Aminopolycarboxylates are well known in the detergent industry andsometimes referred to as aminocarboxylate chelants. They are generallyappreciated as being strong builders.

Chirality is a geometric property of molecules induced by the moleculeshaving at least one chiral centre. A chiral molecule isnon-superimposable on its mirror image. The chiral aminopolycarboxylateas used in the invention can comprise all its molecular mirror images.

Chiral and preferred aminopolycarboxylates are glutamic acidN,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA),ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS),iminodimalic acid (IDM) or a mixture thereof, more preferred are GLDA,MGDA, EDDS or a mixture thereof and even more preferred are GLDA andMGDA or a mixture thereof. Preferably the aminopolycarboxylate as usedin the first solid phase essentially is GLDA and/or MGDA. In case ofGLDA preferably is it predominantly (i.e. for more than 80 molar %)present in one of its chiral forms.

Examples of non-chiral aminopolycarboxylates areethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA),iminodiacetic acid (IDA), diethylenetriaminepentaacetic acid (DTPA),hydroxyethyliminodiacetic acid (HEIDA) aspartic acid diethoxysuccinicacid (AES) aspartic acid-N,N-diacetic acid (ASDA),hydroxyethylene-diaminetetraacetic acid (HEDTA),hydroxyethylethylene-diaminetriacetic acid (HEEDTA), iminodifumaric(IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL),ethylenediaminedifumaric acid (EDDF), ethylenediaminedimalic acid(EDDM), ethylenediamineditartaric acid (EDDT), ethylenediaminedimaleicacid and (EDDMAL), dipicolinic acid. None-chiral aminopolycarboxylatesare preferably present in an amount of at most 10 wt. %, more preferablyat most 5 wt. % and even more preferably essentially absent from thefirst solid phase of the shaped detergent product of the invention.

The first solid phase of the invention preferably comprises from 12 to70 wt. % free acid equivalent of aminopolycarboxylate. More preferably,the aminopolycarboxylate content is from 20 to 68 wt. % free acidequivalent and even more preferably from 35 to 60 wt. % free acidequivalent.

It is preferred that the first solid phase contains at least 12 wt. %,more preferably at least 20 wt. %, even more preferably at least 25 wt.% free acid equivalent of aminopolycarboxylate selected from glutamicacid N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA),ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS),iminodimalic acid (IDM) and combinations thereof. It is highly preferredthat the first solid phase contains at least 12 wt. %, more preferablyat least 20 wt. %, even more preferably at least 25 wt. % free acidequivalent of aminopolycarboxylate selected from GLDA, MGDA, EDDS andcombinations thereof.

Non-Crystalline Organic Acid

The first solid phase of the shaped detergent product inventioncomprises a non-crystalline organic acid other than component a), i.e.,said organic acid not being an aminopolycarboxylate.

As explained herein before, it was unexpectedly discovered that it ispossible to prepare a transparent first solid phase containingaminopolycarboxylate, organic acid and water.

The presence of crystals in the first solid phase can suitably bedetermined by WAXS, using the method set-out in the Examples. Withoutwishing to be bound by theory, it is believed that the molecularinteraction of the aminopolycarboxylate with the acid (although notcovalently bound to it) prevents either of these components fromcrystallizing. Thus, another benefit of the composition according to theinvention is that the composition can be free of further added crystalformation inhibitors.

The organic acid used in the first solid phase according to theinvention can be any organic acid. Particularly good results wereachieved with organic acids being polyacids (i.e. acids having more thanone carboxylic acid group), and more particularly with organic acidswhich are di- or tri-carboxylates.

Another preference is that the organic acids used in the invention havean average molecular mass of at most 500 Dalton, the molecular massbeing based on the free acid equivalent. In any case, preferably theorganic acid is not a polymer-based acid. Even more preferred is thatthe organic acids have from 3 to 25 carbon atoms, preferably 4 to 15carbon atoms.

In general, any organic acid can be used, but in view of consumeracceptance the organic acids preferably are those which are also foundnaturally occurring, such as in plants. As such, organic acids of noteare acetic acid, citric acid, aspartic acid, lactic acid, adipic acid,succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid,fumaric acid, saccharic acids, their salts, or mixtures thereof. Ofthese, of particular interest are citric acid, aspartic acid, aceticacid, lactic acid, succinic acid, glutaric acid, adipic acid, gluconicacid, their salts, or mixtures thereof. Citric acid, lactic acid, aceticacid and aspartic acid are even more preferred. Citric acid and/or itssalt are especially beneficial as, besides acting as builder are alsohighly biodegradable. As such the more preferred non-crystalline organicacid of the invention comprises (and essentially is) citric acid,citrate salt or a mixture thereof. In general, the acids of the organicacids are more preferred than their alkali salt equivalents.

Preferably, the first solid phase comprises from 0.2 to 55 wt. % freeacid equivalent of the acid. More preferred is a total amount of theacid of from 2 to 52 wt. % free acid equivalent, more preferably of from5 to 50 wt. % free acid equivalent and most preferably from 15 to 40 wt.% free acid equivalent.

Better results were achieved with certain weight ratios ofaminopolycarboxylate and the acid in the first solid phase. Therefore itis preferred that the weight ratio of aminopolycarboxylate to acid isfrom 1:2 to 1:0.15, preferably from 1:1.5 to 1:0.4, more preferably from1:1.4 to 1:0.5, based on the weight of the free acid equivalents.

Preferably, the first solid phase contains at least 2 wt. %, morepreferably at least 5 wt. %, even more preferably at least 15 wt. %,most preferably at least 20 wt. % free acid equivalent of an acidselected from acetic acid, citric acid, aspartic acid, lactic acid,adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,maleic acid, fumaric acid, saccharic acids, sulfuric acid, hydrochloricacid and combinations thereof.

Particularly preferred is that the first solid phase contains at least 2wt. %, more preferably at least 5 wt. %, even more preferably at least15 wt. %, most preferably at least 20 wt. % free acid equivalent of adi- and/or tri-carboxylic acid having a molecular weight of less than500 Dalton, more preferably of less than 400 Dalton and most preferablyof less than 300 Dalton.

Most preferably the first solid phase contains at least 2 wt. %, morepreferably at least 5 wt. %, even more preferably at least 15 wt. %,most preferably at least 20 wt. % free acid equivalent of citric acid.

Particularly preferred are combinations of aminopolycarboxylate andorganic acid comprise GLDA and citric acid; or MGDA and citric acid.

It was found that the first solid phase of the present invention can berendered substantially more plastic (less solid) by heating the firstsolid phase to a temperature of at least 50 degrees Celsius. Thisthermoplastic behaviour can suitably be used in the preparation of theshaped detergent product, e.g. by introducing the plasticized firstsolid phase into a mould and solidifying the plasticized phase withinthe mould by cooling.

Also, the plasticized phase may be spread as a layer onto a solidsubstrate followed by cooling to solidify. Also its thermoplasticbehaviour makes it more suitable for extrusion.

Water

The first solid phase according to the invention comprises from 2 to 30wt. % of water. It was surprisingly found that use of such a watercontent provided a solid composition with a good balance of hardness andplasticity. Depending on the water level the first solid phase can be ahard solid (water level of from 2 to 20 wt. %), or a soft solid (waterlevel above 20 to 30 wt. %). The general plasticity and thermoplasticbehaviour offers the significant practical advantage that the solidcomposition can be (machine) worked with a low chance of breakage or offorming cracks. Also, not unimportantly, it can provide an improvedsensory experience when handled by the consumer. Better results wereachieved with from 5 to 25 wt. % of water and better ones still withfrom 6 to 20 wt. % of water. The latter ranges provide a further optimumbetween suitable hardness, reduced brittleness and plasticity. Thewater-activity a_(w) of the first solid phase according to the inventioncan be 0.7 or lower. Preferred is a water-activity a_(w) of at most 0.6,and further preferred of at most 0.5. The preferred lower limit of wateractivity a_(w) may be 0.15.

pH Profile

The first solid phase of the invention preferably has the following pHprofile: the pH of a solution of the first solid phase made bydissolving the first solid phase in water in a 1:1 weight ratio is atmost 10.0, as measured at 25 degrees Celsius. Such a pH profile improvesstability of the first solid phase. Particularly good results wereachieved for said pH profile being at most 9.0, more preferably at most8.0. Many detergents products are overall alkaline. As such, forpractical reasons and to increase formulation freedom, preferably the pHof a solution made by dissolving 1 wt. % of the first solid phase inwater is at least 5.0 and more preferably at least 6.0 and mostpreferably at least 6.5.

Non-Crystalline Water-Soluble Component

The first solid phase of the shaped detergent product may comprise atmost 50 wt. % non-crystalline water-soluble component other thancomponent a) or component b). Said non-crystalline water-solublecomponent can be liquid or solid, when considered in pure form, butpreferably is a solid. If in the form of a liquid (e.g. liquidsurfactant), it is preferably present in an amount of up to 20 wt. %,more preferably up to 10 wt. % and even more preferably up to 5 wt. %.

Preferably, the first solid phase comprises 5 to 45 wt. %, morepreferably 10 to 40 wt. %, even more preferably 15 to 35 wt. %, mostpreferably 25 to 30 wt. % non-crystalline water-soluble component.

In a preferred embodiment, the first solid phase contains at least 10wt. % of water-soluble component selected from polycarboxylate polymer,sulfonated polymer and combinations thereof. In case the water-solublecomponent is an acid or a salt, this weight percentage refers to thefree acid equivalent wt. %.

The term “polycarboxylate polymer” here is used to also cover the acidform and is different from the organic acid that is present in the firstsolid phase. The addition of polycarboxylate polymer was shown tosurprisingly further improve the plasticity of the first solid phase aswell as raise the glass transition temperature (T_(g)) of the firstsolid phase. The improved plasticity is beneficial as it makes the firstsolid phases easier to (mechanically) work and makes it easier tomanufacture detergent product comprising the first solid phase. A higherglass transition temperature is beneficial as it aids stability of thefirst solid phase during storage and handling, in particular in view oftemperature stresses. That being said a glass transition temperaturewhich is not too high will aid quick dissolution of the product in warmwater as it helps to liquefy the first solid phase during use byincreasing surface area.

Preferably, the glass transition temperature (T_(g)) of the first solidphase is less than 80 degrees Celsius, more preferably from 10 to 60degrees Celsius, even more preferably from 15 to 50 degrees Celsius andmost preferably from 20 to 40 degrees Celsius.

According to a particularly preferred embodiment, the first solid phaseof the shaped detergent product contains at least 5 wt. %, morepreferably at least 10 wt. %, even more preferably at least 15 wt. % andmost preferably at least 25 wt. % polycarboxylate polymer, as based onthe free-acid equivalent.

Suitable polycarboxylate polymers have an average molar mass Mw of from500 to 500.000. They may be modified or unmodified, but preferably areunmodified. Also they can be co-polymers or homopolymers, althoughhomopolymers are considered more beneficial.

Surprisingly, it was observed that if the first solid phase of theshaped detergent product comprised polycarboxylate polymer,hygroscopicity was reduced. This reduction was more pronounced if thepolycarboxylate polymer used was of lower molecular weight. Having areduced hygroscopicity is of course beneficial as it aids in improvingthe stability of the shaped detergent product, and generally increasesshelf life. Polycarboxylate polymers having an average molar mass (Mw)of from 900 to 100.000, more preferably 1100 to 10.000 gave betterresults in terms of further improving the glass transition temperature(T_(g)), the plasticity and the hygroscopicity.

In a preferred embodiment, the first solid phase comprises at least 5wt. %, more preferably at least 10 wt. %, even more preferably at least15 wt. % and most preferably at least 25 wt. % free acid equivalent ofpolycarboxylate polymer selected from polyacrylate, copolymers ofpolyacrylate, polymaleate, copolymers of polymaleate, polymethacrylate,copolymers of polymethacrylate, polymethyl-methacrylate, copolymers ofpolymethyl-methacrylate, polyaspartate, copolymers of polyaspartate,polylactate, copolymers of polylactate, polyitaconates, copolymers ofpolyitaconates and combinations thereof.

Highly preferred polycarboxylate polymers are polyacrylates. Suitablepolyacrylates are commercially available, such as from BASF under thetradename Sokalan PA 13 PN, Solakan PA 15, Sokalan PA 20 PN, Sokalan PA20, Sokalan PA 25 PN, Sokalan PA 30, Sokalan 30 CL, Sokalan PA 40,Sokalan PA 50, Sokalan PA 70 PN, Sokalan PA 80 S and Sokalan PA 110 S.PN stands for partially neutralized, S for free acid forms. Preferredare polyacrylates which are partially or fully neutralized. Thesecommercially available polyacrylates differ in other respects in theiraverage molar mass (higher numbers represent higher average molar massMw).

As such highly preferred for use in the first solid phase of inventionare polyacrylates having the following combined properties:

-   -   present in an amount of from 10 to 40 wt. %, based on the free        acid equivalent; and    -   which are partially or fully neutralized; and    -   which have an average molar mass (Mw) of from 500 to 500.000;        and    -   which are homopolymers.

Given the above it follows that still more preferred are polyacrylateshaving the following combined properties:

-   -   used in an amount of from 10 to 40 wt. %, based on the free acid        equivalent; and    -   which are partially or fully neutralized; and    -   which have an average molar mass (Mw) of from 900 to 100.000;        and    -   which are homopolymers.

The sulfonated polymer that preferably are employed in accordance withthe present invention can be a copolymer or a homopolymer. Preferablythe sulfonated polymer is a copolymer. Suitable sulfonated polymers havea mass averaged molecular mass of 3,000 to 50,000, more preferably from4,500 to 35,000. Surprisingly, it was observed that if the first solidphase comprised sulfonated polymer, hygroscopicity was reduced. Having areduced hygroscopicity is of course beneficial as it aids in improvingthe stability of the shaped detergent product, and generally increasesshelf life.

In a preferred embodiment, the first solid phase comprises at least 0.3wt. %, more preferably at least 0.6 wt. %, even more preferably at least2 wt. % and most preferably at least 3 wt. % free acid equivalent ofsulfonated polymer comprising polymerized units of one or moreunsaturated sulfonate monomers selected from 2-acrylamidomethyl-1-propanesulfonic acid,2-methacrylicamido-2-methyl-1-propanesulphonic acid,3-methacrylamido-2-hydroxy-propanesulphonic acid, allylsulphonic acid,methallylsulphonic acid, allyloxybenzenesulphonic acid.methallyloxybenzenesulphonic acid,2-hydroxy-3-(2-propenyloxy)propanesulphonic acid,2-methyl-2-propene-1-sulphonic acid, styrene sulphonic acid,vinylsulphonic acid, 3-sulphopropyl acrylate, 3-sulphopropylmethacrylate, sulphomethylacrylamide, sulphomethylmethacrylamide.

More preferably, the first solid phase comprises at least 0.3 wt. %,more preferably at least 0.6 wt. %, even more preferably at least 2 wt.% and most preferably at least 3 wt. % free acid equivalent ofsulfonated polymer comprising polymerized units of one or moreunsaturated sulfonate monomers selected from 2-acrylamidomethyl-1-propanesulfonic acid,2-methacrylicamido-2-methyl-1-propanesulphonic acid,3-methacrylamido-2-hydroxy-propanesulphonic acid.

More preferably, the first solid phase comprises at least 0.3 wt. %,more preferably at least 0.6 wt. %, even more preferably at least 2 wt.% and most preferably at least 3 wt. % free acid equivalent ofsulfonated polymer comprising polymerized units of 2-acrylamidomethyl-1-propanesulfonic acid.

In accordance with another preferred embodiment, the first solid phasecomprises at least 0.3 wt. %, more preferably at least 0.6 wt. %, evenmore preferably at least 2 wt. % and most preferably at least 3 wt. %free acid equivalent of sulfonated polymer comprising polymerized unitsof one or more unsaturated sulfonate monomers represented by thefollowing formula:

CH₂═CR¹—CR²R³—O—C₄H₃R⁴—SO₃X

wherein

R¹, R², R³, R⁴ independently represent C₁-C₆ alkyl or hydrogen; Xrepresents hydrogen or alkali.

According to a particularly preferred embodiment, the sulfonated polymeris a copolymer comprising polymerized units of monoethylenicallyunsaturated C₃-C₆ monocarboxylic acid. More preferably, the sulfonatedcopolymer comprises the following monomers in polymerised form:

-   -   50-90 wt. % of one or more monoethylenically unsaturated C₃-C₆        monocarboxylic acid;    -   10-50 wt. % of unsaturated sulfonate monomers as defined herein        before.

According to another preferred embodiment, the monoethylenicallyunsaturated C₃-C₆ monocarboxylic acid in the sulfonated copolymer areselected from acrylic acid, meth(acrylic) acid and combinations thereof.

As such highly preferred for use in the first solid phase of inventionare sulfonated copolymers having the following combined properties:

-   -   used in an amount of from 2 to 15 wt. %, based on the free acid        equivalent; and    -   which are partially or fully neutralized; and    -   which have an average molar mass (Mw) of from 3,000 to 50,000    -   which comprised the following monomers in polymerised form:        50-90 wt. % of one or more monoethylenically unsaturated C₃-C₆        monocarboxylic acid; and 10-50 wt. % of unsaturated sulfonate        monomers selected from 2-acrylamido methyl-1-propanesulfonic        acid, 2-methacrylicamido-2-methyl-1-propanesulphonic acid,        3-methacrylamido-2-hydroxy-propanesulphonic acid

Given the above it follows that still more preferred are sulfonatedcopolymers having the following combined properties:

-   -   used in an amount of from 3 to 12 wt. %, based on the free acid        equivalent; and    -   which are partially or fully neutralized; and    -   which have an average molar mass (Mw) of from 4,500 to 35,000.    -   which comprised the following monomers in polymerised form:        50-90 wt. % of acrylic acid and/or meth(acrylic acid); and 10-50        wt. % of 2-acrylamido methyl-1-propanesulfonic acid

Shaped Detergent Product

The first solid phase of the shaped detergent product is preferablyvisually distinct from the remainder of the detergent product. Thedetergent product is advantageously a unit-dose detergent product.

Preferably, the first solid phase that is present in the shapeddetergent product is present in at least one coherent volume of from 0.1to 20 cm³, more preferably from 0.2 to 15 cm³, even more preferably from0.4 to 10 cm³, most preferably from 0.5 to 5 cm³. Said preferred volumesallows the first solid phase of the invention to be easily visible tothe naked eye, allowing it to be better appreciated for its visualappeal. The first solid phase may be present in any suitable form suchas a layer (skin/coating), bar, a cube or the like.

The first solid phase preferably has a maximum Transmittance within thewavelength range of 400 to 700 nm of at least 5%, more preferably of atleast 10%, even more preferably of at least 20%, yet more preferably ofat least 25% and most preferably of least 30%. Preferably the firstsolid phase has an average Transmittance in the wavelength range of 400to 700 nm of at least 5%, more preferably of at least 10%, even morepreferably of at least 20% and most preferably of at least 25%.

In a preferred embodiment, the shaped detergent product comprises 10 to90 wt. % of the first solid phase and 10 to 90 wt. % of one or moreother solid phases. Examples of shaped detergent products containing thefirst solid phase in combination with one or more other solid phases aretablets that are coated with the first solid phase. Another example aremulti-layered tablets containing one or more layers of the first solidphase and one or more layers of a second solid phase.

Preferably, the second solid phase is visually distinct from the firstsolid phase.

According to a particularly preferred embodiment, the first solid phaseis translucent or transparent and the second solid phase is opaque.

Preferably, the shaped detergent product of the invention is a machinedish wash detergent product, a laundry detergent product or a toiletrim-block detergent product. Most preferably, the shaped detergentproduct is a machine dish wash detergent product.

In case of machine dish wash detergent products, the particularlypreferred amount of the first solid phase is from 5 to 60 wt. %, morepreferably 10 to 50 wt. % and even more preferably 15 to 40 wt. %.

In case of laundry detergent products, the particularly preferred amountof the first solid phase of the invention is from 10 to 60, morepreferably 20 to 50 wt. %, and even more preferably, 25 to 35 wt. %.

In case of toilet bowl rim detergent products, the particularlypreferred amount of the first solid phase of the invention is from 10 to85 wt. %, more preferably 20 to 80 wt. % and even more preferably 40 to70 wt. %.

The distinctiveness of the first solid phase of the shaped detergentproduct can be enhanced by a suitable distinctive colouring. This can bedone by making it of more intense or of less intense colour (e.g.colourless). Preferably of course when colouring is applied, thetranslucency is maintained to an appreciable extent. Generallycolourants, such as dyes and/or pigments are effective in low amountsand as such this is typically not problematic. In any case, it isparticularly envisioned that the first solid phase of the invention isused in a detergent product and adds to the visual appeal thereof.

The first solid phase can be present in the detergent product of theinvention in any suitable shape or shapes, such as in one or morelayers, lines (e.g. rods, beams), spherical or cuboid shapes orcombinations thereof. Preferred shapes are the following: cuboid,cylinder, sphere, bar, X-bar, pyramid, prism, cone, dome and (circular)tube. Of these more preferred shapes are bar, X-bar, cylinder, cuboid,(circular) tube and sphere.

Preferably the shaped detergent product has a unit weight of 5 to 50grams, more preferably a unit weight of 10 to 30 grams, even morepreferably a unit weight of 12 to 25 grams.

Preferably, the shaped detergent product is a tablet.

Whatever the geometric arrangement of the first solid phase within theoverall detergent product, it is preferred that at least part the solidcomposition forms part of the surface of the detergent product. Morepreferably, at least 10%, 20%, 30%, 40% more preferably at least 50% ofthe surface area of the detergent product is formed by the solidcomposition. Preferably at most 95%, 90% and more preferably at most 85%of the surface area of the detergent product is formed by the solidcomposition.

The first solid phase of the invention in the detergent product may actas a matrix and hold part, or the whole, of the further ingredients inthe detergent product. In this sense, the solid composition of theinvention may be used to form a (partial) skin. Advantageously the solidcomposition acts as a translucent matrix holding one or more visuallydistinct bodies. The bodies being preferably in the shape of spheres orcubes. The bodies being preferably coloured.

In general, the skilled person is endowed with the capability to use thefirst solid phase of the invention to his advantage when making moreappealing detergent products. In particular the first solid phase can beused to provide a (partially) translucent detergent product and/or toprovide a (partially) glossy detergent product. As described above, waysof using the first solid phase in a detergent product in which the solidremains visible and can be appreciated for it translucent and/or glossynature are highly preferred.

Further Ingredients

The first solid phase of the invention may, depending on theaminopolycarboxylate and acid used, be colored and for example have ayellowish tinge. The translucency of such first solid phase can befurther improved by adding an opposing colorant of the color wheel,which is preferably a dye. For example, yellow opposes blue on the colorwheel, and violet opposes green. This will render the first solid phasein essence to be more colorless, which can be preferred. It is notedthat typical dyes need be added in relatively small amounts to beeffective. Hence their level is suggested not to be above 0.5 wt. % andpreferably is at most 0.2 wt. %.

The detergent product according to the invention comprises the firstsolid phase according to the invention. The detergent product inaddition comprises, preferably in the other part(s), at least onefurther detergent active, and preferably one or more of enzymes, enzymestabilizers, bleaching agents, bleach activator, bleach catalyst, bleachscavengers, drying aids, silicates, metal care agents, colorants,perfumes, lime soap dispersants, anti-foam, anti-tarnish, anti-corrosionagents, surfactants and further builders.

Further Builders

Further builder materials may be selected from 1) calcium sequestrantmaterials, 2) precipitating materials, 3) calcium ion-exchange materialsand 4) mixtures thereof. Examples of calcium sequestrant buildermaterials include alkali metal polyphosphates, such as sodiumtripolyphosphate and organic sequestrants, such as ethylene diaminetetraacetic acid. Examples of precipitating builder materials includesodium orthophosphate and sodium carbonate. Preferably, the detergentproduct comprises sodium carbonate in the range from 5 to 50 wt. %, mostpreferably 10 to 35 wt. %.

Examples of calcium ion-exchange builder materials include the varioustypes of water-insoluble crystalline or amorphous aluminosilicates, ofwhich zeolites are the best known representatives, e.g. zeolite A,zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y andalso the zeolite P-type as described in EP-A-0,384,070.

The detergent product may also contain 0-65% of a builder or complexingagent such as ethylenediaminetetraacetic acid,diethylenetriamine-pentaacetic acid, alkyl- or alkenylsuccinic acid,nitrilotriacetic acid or the other builders mentioned below. Manybuilders are also bleach-stabilising agents by virtue of their abilityto complex metal ions. Zeolite and carbonate (carbonate (includingbicarbonate and sesquicarbonate) are preferred further builders.

The builder may be crystalline aluminosilicate, preferably an alkalimetal aluminosilicate, more preferably a sodium aluminosilicate. This istypically present at a level of less than 15 wt. %. Aluminosilicates arematerials having the general formula: 0.8-1.5 M₂O. Al₂O₃. 0.8-6 SiO₂,where M is a monovalent cation, preferably sodium. These materialscontain some bound water and are required to have a calcium ion exchangecapacity of at least 50 mg CaO/g. The preferred sodium aluminosilicatescontain 1.5-3.5 SiO₂ units in the formula above. They can be preparedreadily by reaction between sodium silicate and sodium aluminate, asamply described in the literature. The ratio of surfactants toalumuminosilicate (where present) is preferably greater than 5:2, morepreferably greater than 3:1.

Alternatively, or additionally to the aluminosilicate builders,phosphate builders may be used. In this invention the term ‘phosphate’embraces diphosphate, triphosphate, and phosphonate species. Other formsof builder include silicates, such as soluble silicates, metasilicates,layered silicates (e.g. SKS-6 from Hoechst). However, preferably thedetergent product is a non-phosphate built detergent product, i.e.,contains less than 1 wt. % of phosphate and preferably essentially nophosphate.

In view of the environmental concerns associated with the use of highlevels of phosphorous based builders in detergent compositions it ispreferred that the detergent product according to the inventioncomprises at most 5 wt. %, more preferably at most 1 wt. % andparticularly essentially no phosphorous based builders. Examples ofphosphorous based builders are 1-hydroxyethane-1,1-diphosphonic acid(HEDP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP),ethylenediaminetetra-methylenephosphonate (EDTMP), tripolyphosphate,pyrophosphate.

Alkali carbonate is appreciated in view of its double-function asbuilder and buffer and is preferably present in the detergent product.If present the preferred amount of alkali carbonate in the detergentproduct is from 2 to 75 wt. %, more preferably from 3 to 50 wt. % andeven more preferably from 5 to 20 wt. %. Such level of alkali carbonateprovides good Ca²⁺ and Mg²⁺ ion scavenging for most types of waterhardness levels, as well as other builder effects, such as providinggood buffering capacity. The preferred alkali carbonates are sodium-and/or potassium carbonate of which sodium carbonate is particularlypreferred. The alkali carbonate present in the detergent product of theinvention can be present as such or as part of a more complex ingredient(e.g. sodium carbonate in sodium percarbonate).

Surfactant

The shaped detergent product of the invention comprises 0.5 wt. %surfactant, preferably 1 to 70 wt. %, more preferably 2 to 50 wt. % ofsurfactant. The surfactant can be non-ionic or anionic.

In case of machine dish wash detergent products, the particularlypreferred amount of surfactant is from 0.5 to 25 wt. %, preferably 2 to15 wt. %. In case of toilet bowl rim detergent products, theparticularly preferred amount of surfactant is from 0.5 to 55 wt. %,preferably 10 to 40 wt. %. In case of laundry detergent products, theparticular preferred amount of surfactant is from 2 to 70 wt. %,preferably 10 to 35 wt. %.

The nonionic and anionic surfactants of the surfactant system may bechosen from the surfactants described “Surface Active Agents” Vol. 1, bySchwartz & Perry, lnterscience 1949, Vol. 2 by Schwartz, Perry & Berch,lnterscience 1958, in the current edition of “McCutcheon's Emulsifiersand Detergents” published by Manufacturing Confectioners Company or in“Tenside-Taschenbuch”, H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.Preferably the surfactants used are saturated.

Non-Ionic Surfactants

Suitable non-ionic surfactants which may be used include, in particular,the reaction products of compounds having a hydrophobic group and areactive hydrogen atom, for example, aliphatic alcohols, acids, amidesor alkyl phenols with alkylene oxides, especially ethylene oxide eitheralone or with propylene oxide.

Preferably low-foaming nonionic surfactants are used particularly fromthe group of alkoxylated alcohols. Alkoxylated, advantageouslyethoxylated, in particular primary alcohols with preferably 8 to 18 Catoms and on average 1 to 12 mol of ethylene oxide (EO) per mol ofalcohol, in which the alcohol residue may be linear or preferablymethyl-branched in position 2 or may contain linear and methyl-branchedresidues in the mixture, as are usually present in oxo alcohol residues,are preferably used as nonionic surfactants. In particular, however,alcohol ethoxylates with linear residues prepared from alcohols ofnatural origin with 12 to 18 C atoms, for example from coconut, palm,tallow fat or oleyl alcohol, and on average 2 to 8 mol of EO per mol ofalcohol are preferred. The preferred ethoxylated alcohols include forexample C₁₂₋₁₄ alcohols with 3 EO to 4 EO, C₉₋₁₂ alcohol with 7 EO,C₁₃₋₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C₁₂₋₁₈ alcohols with 3EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C₁₂₋₁₄alcohol with 3 EO and C₁₂₋₁₉ alcohol with 5 EO. Preferred tallow fattyalcohols with more than 12 EO have from 60 to 100 EO, and morepreferably from 70 to 90 EO. Particularly preferred tallow fattyalcohols with more than 12 EO are tallow fatty alcohols with 80 EO.

Nonionic surfactants from the group of alkoxylated alcohols,particularly preferably from the group of mixed alkoxylated alcohols andin particular from the group of EO-AO-EO nonionic surfactants, arelikewise particularly preferentially used. Preferably used nonionicsurfactants originate from the groups comprising alkoxylated nonionicsurfactants, in particular ethoxylated primary alcohols and mixtures ofthese surfactants with structurally complex surfactants such aspolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO). Such(PO/EO/PO) nonionic surfactants are furthermore distinguished by goodfoam control.

The most preferred nonionic surfactants are according to the formula:

wherein n is from 0 to 5 and m from 10 to 50, more preferably wherein nis from 0 to 3 and m is from 15 to 40, and even more preferably whereinn is 0 and m is from 18 to 25. Surfactants according to this formulawere particularly useful in reducing spotting of dishware treated in amachine dish washer. Preferably at least 50 wt. % of the nonionicsurfactant comprised by the detergent product of the invention isnonionic surfactant according to this formula. Such nonionic surfactantsare commercially available, e.g. under the tradename Dehypon WET(Supplier: BASF) and Genapol EC50 (Supplier Clariant).

The shaped detergent product of the invention preferably comprises from0.5 to 15 wt. % of nonionic surfactant. The more preferred total amountof nonionic surfactants is from 2.0 to 8 wt. % and even more preferredis an amount of from 2.5 to 5.0 wt. %. The nonionic surfactant used inthe detergent product of the invention can be a single nonionicsurfactant or a mixture of two or more non-ionic surfactants.

The nonionic surfactant is preferably present in amounts of 25 to 90 wt.% based on the total weight of the surfactant system. Anionicsurfactants can be present for example in amounts in the range from 5 to40 wt. % of the surfactant system.

Anionic Surfactants

Suitable anionic surfactants which may be used are preferablywater-soluble alkali metal salts of organic sulphates and sulphonateshaving alkyl radicals containing from about 8 to about 22 carbon atoms,the term alkyl being used to include the alkyl portion of higher acylradicals. Examples of suitable synthetic anionic surfactants are sodiumand potassium alkyl sulphates, especially those obtained by sulphatinghigher C8 to C18 alcohols, produced for example from tallow or coconutoil, sodium and potassium alkyl C9 to C20 benzene sulphonates,particularly sodium linear secondary alkyl 010 to C15 benzenesulphonates; and sodium alkyl glyceryl ether sulphates, especially thoseethers of the higher alcohols derived from tallow or coconut oil andsynthetic alcohols derived from petroleum. The preferred anionicsurfactants are sodium 011 to C15 alkyl benzene sulphonates and sodiumC12 to C18 alkyl sulphates. Also applicable are surfactants such asthose described in EP-A-328 177 (Unilever), which show resistance tosalting-out, the alkyl polyglycoside surfactants described in EP-A-070074, and alkyl monoglycosides.

Bleaching System

It is preferred that the shaped detergent product according to theinvention comprises at least 5 wt. %, more preferably at least 8 wt. %and even more preferably at least 10 wt. % of bleaching agent by totalweight of the product. The bleaching agent preferably comprises achlorine-, or bromine-releasing agent or a peroxygen compound.Preferably, the bleaching agent is selected from peroxides (includingperoxide salts such as sodium percarbonate), organic peracids, salts oforganic peracids and combinations thereof. More preferably, thebleaching agent is a peroxide. Most preferably, the bleaching agent is apercarbonate.

The shaped detergent product of the invention may contain one or morebleach activators such as peroxyacid bleach precursors. Peroxyacidbleach precursors are well known in the art. As non-limiting examplescan be named N,N,N′,N′-tetraacetyl ethylene diamine (TAED), sodiumnonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzenesulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) asdescribed in US-A-4,751,015.

Preferably the shaped detergent product comprises a bleach catalyst.Particularly preferred is a bleach catalyst which is a manganesecomplex, such as Mn-Me TACN, as described in EP-A-0458397, and/or thesulphonimines of U.S. Pat. Nos. 5,041,232 and 5,047,163. It isadvantageous that the bleach catalyst is physically separated in thedetergent product from the bleach (to avoid premature bleachactivation). Cobalt or iron catalysts can also be used.

Enzymes

The shaped detergent product of the invention further preferablycomprises one or more enzymes chosen from proteases, alpha-amylases,cellulases, lipases, peroxidases/oxidases, pectate lyases, andmannanases. Particularly preferred is protease, amylase or a combinationthereof. If present the level of each enzyme is from 0.0001 to 1.0 wt.%, more preferably 0.001 to 0.8 wt. %.

Silicates

Silicates are known detergent ingredients, and often included to providedish wash care benefits, and reduce corrosion of dishware. Particularlypreferred silicates are sodium disilicate, sodium metasilicate andcrystalline phyllosilicates or mixtures thereof. If present the totalamount of silicates preferably is from 1 to 15 wt. %, more preferablyfrom 2 to 10 wt. % and even more preferably from 2.5 to 5.0 wt. % byweight of the shaped detergent product.

Perfume

Preferably the shaped detergent product of the invention comprises oneor more colorants, perfumes or a mixture thereof in an amount of from0.0001 to 8 wt. %, more preferably from 0.001 to 4 wt. % and even morepreferably from 0.001 to 1.5 wt. %.

Perfume is preferably present in the range from 0.1 to 1 wt. %. Manysuitable examples of perfumes are provided in the CTFA (Cosmetic,Toiletry and Fragrance Association) 1992 International Buyers Guide,published by CFTA Publications and OPD 1993 Chemicals Buyers Directory80th Annual Edition, published by Schnell Publishing Co. In perfumemixtures preferably 15 to 25 wt. % are top notes. Top notes are definedby Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]).Preferred top-notes are selected from citrus oils, linalool, linalylacetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

Shading Dyes

In particular for laundry detergent compositions according to theinvention, it is preferred that these comprise shading dye. Shading dyesare, for example, added to laundry detergent formulations to enhance thewhiteness of fabrics. Shading dyes are preferably blue or violet dyeswhich are substantive to fabric. A mixture of shading dyes may be usedand indeed are preferred for treating mixed fiber textiles. Thepreferred amount of shading dyes is from 0.00001 to 1.0 wt. %,preferably 0.0001 to 0.1 wt. % and particularly an amount of 0.001 to0.01 wt. % is preferred. Shading dyes are discussed in WO2005/003274,WO2006/032327, WO2006/032397, WO2006/045275, WO2006/027086,WO02008/017570, WO 2008/141880, WO2009/132870, WO2009/141173, WO2010/099997, WO 2010/102861, WO2010/148624, WO2008/087497 andWO2011/011799.

Form of the Shaped Detergent Product

Due to the presence of the first solid phase, the shaped detergentproduct at least contains a solid part. The remainder of the detergentproduct can also be non-solid, such as in the form of a liquid, butpreferably contains at least one further solid part.

The detergent product is preferably provided as a water-soluble orwater-dispersible unit dose. Particularly preferred unit doses are inthe form of pouches, which comprise at least one further non-shapestable ingredient, such as a liquid and/or powder; or in the form oftablets. For ease of use, the unit dose is sized and shaped as to fit inthe detergent cup of a conventional house-hold machine dishwasher,laundry machine or toilet-rim holder, as is known in the art.

Advantageous unit dose pouches preferably have more than onecompartment.

Advantageous unit dose tablets are those which have more than onevisually distinct tablet region. Such regions can be formed by e.g. twodistinct (colored) layers or a tablet having a main body and a distinctinsert, such as forming a nested-egg. However oriented, one benefit ofusing multi-compartmental pouches/multi-region tablets is that it can beused to reduce/prevent undesired chemical reactions between two or moreingredients during storage by physical segregation.

Preferably the unit dose detergent product is wrapped to improve hygieneand consumer safety. The wrapper advantageously is based onwater-soluble film which preferably a polyvinylalcohol (PVA) based film.Such wrapping prevents direct contact of the detergent product with theskin of the consumer when placing the unit dose in the detergentcup/holder of a e.g. machine dishwasher. A further benefit of course isthat the consumer also does not need to remove a water-soluble wrappingbefore use.

The detergent products according to the invention can be made usingknown methods and equipment in the field of detergent manufacturing. Thedetergent product according to the invention can be made by combiningthe first solid phase of the invention together with the remainder ofthe detergent ingredients. In view of making tablets, a particularlypreferred way of combining is by pressing the first solid phase of theinvention onto (or into) the remainder of the tablet ingredients and/orby adding the first solid phase in heated (liquid) form.

Preferred Detergent Product Formulations

A highly preferred general detergent product formulation is as follows:

Ingredient Amount (wt. %) First solid phase according to the invention10 to 80 Surfactant 0.5 to 70  Phosphate at most 1.0 Preferably perfumeand colorants in a 0.0001 to 8.0   combined amount of

In case of a machine dish wash detergent product the product ispreferably a unit-dose tablet with the following composition:

Ingredient Amount (wt. %) First solid phaseaccording to the invention 15to 40  Further builder, preferably alkali carbonate 5 to 20 Non-ionicsurfactant 0.5 to 15   Enzyme 0.001 to 0.8   Silicates 1 to 10 Bleachingagent + bleach activator + 2 to 20 bleach catalyst Phosphate at most 1.0Preferably perfume and colorants in a 0.001 to 1.5   combined amount of

In case of a toilet rim detergent product the product is preferably is asolid block composition, e.g. without comprising liquid parts and/orpowder/granular parts and even more preferably having the followingcomposition:

Ingredient Amount (wt. %) First solid phase according to the invention40 to 70 Anionic surfactant 10 to 40 Non-ionic surfactant 0.5 to 15 Bleaching agent + bleach activator  2 to 20 Total amount of phosphate atmost 1.0 Preferably perfume and colorants in a 0.001 to 8    combinedamount of

In case of a laundry detergent product these advantageously have thefollowing composition:

Ingredient Amount (wt. %) First solid phase according to the invention 5 to 35 Surfactant 10 to 35 Enzyme 0.001 to 0.8  Phosphate at most 1.0Preferably perfume and colorants in a 0.001 to 4    combined amount of

Process to Manufacture the First Solid Phase of the Shaped DetergentProduct

Another aspect of the invention relates to a process of preparing thefirst solid phase, said process comprising the steps of:

-   -   I. providing an aqueous solution comprising        aminopolycarboxylate, acid and water-soluble component; and    -   II. removing water from the aqueous solution.

In a preferred embodiment of the process of the invention, the processof manufacture comprises the steps of:

-   -   II. removing water from the aqueous solution by evaporation at a        temperature of at least 50° C. to produce a liquid desiccated        mixture having a water content of not more than 30 wt. %; and    -   III. reducing the temperature of the desiccated mixture to less        than 25° C. to obtain the shaped detergent product.

The process to manufacture the first solid phase according of theinvention, has the benefit of being both simple, economical and omitsthe need for adding further crystal formation inhibitors.

Step I. of the process according to the invention is to provide anaqueous solution comprising:

-   -   a) non-crystalline chiral aminopolycarboxylate; and    -   b) non-crystalline organic acid different from a).

The combining of the ingredients at Step I. can be done in any order.The amount of water to be used in providing the aqueous solutionbeneficially is sufficient to fully dissolve the ingredients a) and b)at boiling temperature to simplify processing. Both theaminopolycarboxylate and the organic acid may be added as a separatepre-made aqueous solutions, which is preferred to further simplifyprocessing. As indicated a preferred Step I. adds a) as (partially)alkali salt and b) as acid. Addition of extra water and/or applicationof heat may be required to fully dissolve the ingredients as precipitatemay form when the aminopolycarboxylate is combined with acid.

Heat may be applied to (more quickly) dissolve the ingredients a) andb). Applying heat at Step I. is preferred as it not only reduces thetime to dissolve (if necessary) the ingredients a) and b), as it mayalso reduce the amount of water needed to provide the solution, savingcosts. Also having less water in the solution provided at Step I. cansave time for completing Step II. of the process. Preferably at Step I.an aqueous solution is provided having a temperature of at least 50,more preferably of at least 70, even more preferably of at least 95degrees Celsius and most preferably of at least 100 degrees Celsius.

The aqueous solution at Step I. should be homogenous at least inrespects of the aminopolycarboxylate, the acid and the water. Morepreferably, the aqueous solution is completely homogeneous. As such itis particularly preferred that the aqueous solution of Step I. issubjected to physical mixing. The aqueous solution provided at Step I.may be viscous.

Adding a lot of water at Step I. means more water needs to be removed atStep II. requiring additional time and/or energy. As such preferably theaqueous solution provided at Step I comprises from 40 to 95 wt. % ofwater, preferably from 45 to 85 wt. %.

The first solid phase is characterised by a pH profile of at most 10.0,based on an a solution of the first solid phase in water in a 1:1 firstsolid phase:water weight ratio, as measured at 25 degrees Celsius. Thiscan be easily achieved by suitably adjusting the pH of the aqueoussolution accordingly, preferably at Step I according to conventionalmeans. For example, a balanced use of acid or (partially) neutralizedsalts forms of the ingredients a) and b) can be applied.

In Step II. of the process water is removed from the aqueous solutionprovided at Step I. by evaporation at a temperature of at least 50degrees Celsius, to provide a water content of from 2 to 30 wt. %.Preferably, water is removed from the aqueous solution by evaporation ata temperature of at least 70 degrees Celsius, more preferably at least95 degrees Celsius and most preferably at least 100 degrees Celsius.

The preferred way of removing water at Step II. is by applyingsufficient heat to bring the aqueous solution provided at Step I. to aboil. This allows fast water removal which is advantageous to obtain thebenefits of the first solid phase according to the invention. As suchthe water removal may be done by any suitable means but preferably issuch that the water removal is on-par with boiling at otherwise standardambient conditions or faster.

It is preferred that Step II. does not involve spray-drying.Spray-drying is considered to promote crystal formation and thus toreduce the translucency of the resulting solid phase.

In Step III. the temperature of the desiccated mixture is reduced toless than 25° C. to obtain a solid phase. Preferably the temperature isreduced to from 20 to 25 degrees Celsius. Step III. can be performed usepassive or active cooling. Active cooling may be done using anyconventional means such as by refrigeration.

In a particularly preferred Step III., the cooling of the desiccatedmixture is achieved by heat exchange with the remainder of the detergentproduct parts. In this sense, it is particularly preferred that the‘first solid phase’ is applied in liquid/viscous form having an elevatedtemperature, onto the remainder of the detergent product and allowed tosolidify in situ to (further) solidify. It is a further surprisingbenefit afforded by the first solid phase of to the invention: it can bere-heated to increase its plasticity for ease of machine working.

Preferably, the first solid phase according to the invention isobtainable by the process according to the invention.

Unless otherwise indicated, preferred aspects in the context of the oneaspect of the invention (e.g. the first solid phase) are also applicableas preferred aspects in the context of one of the other aspects of theinvention mutatis mutandis.

The invention is now illustrated by the following non-limiting examples.

EXAMPLES

Analytical Methods

X-Ray Diffraction (XRD)

XRD was used to detect presence of crystalline material in the firstsolid phase using to the Wide-Angle X-ray Scattering technique (WAXS).XRD was carried out using a D8 Discover X-Ray Diffractometer from BrukerAXS (activa number: 114175). The XRD measurements was performed usingthe following settings:

2θ (7-55°) Theta 1 7.000 Theta 2 10.000/25.000/40.000 X-ray generator(kV/μA) 50/1000 Time (sec) 300 Collimator (mm) 1 Detector distance (cm)32.5 Tube Anode Cu

Differential Scanning Calorimetry

Differential Scanning calorimetry (DSC) was used to measure the glasstransition temperature (Tg) of the first solid phase. The equipment usedof the DSC analysis was a Perkin Elmer power compensated DSC8000equipped with an Intracooler III as cooling means. The stainless-steelsample pan was used which is provided with the equipment by the Supplierand filled according to Supplier instructions with material to beanalyzed. The amount of material added to the sample pan (sample weight)was from 10 to 40 mg. The following settings were used in running themeasurement:

DSC Hold for 1.0 min at 20.00° C.; temperature Cool from 20.00° C. to−20.00° C. at 10.00° C./min; regime Hold for 2.0 min at −20.00° C.; Heatfrom −20.00° C. to 90.00° C. at 5.00° C./min; Hold for 2.0 min at 90.00°C; Cool from 90.00° C. to −20.00° C. at 10.00° C./min; Hold for 2.0 minat −20.00° C.; Heat from −20.00° C. to 90.00° C. at 5.00° C./min;Atmosphere Nitrogen 20 ml/min

The Tg of the samples was measured with the second heating (i.e. thelast heating step in the DSC temperature regime).

Examples 1-8

Solid phases according to the invention were made starting from anaqueous solution having a composition as set out in the following TableA.

TABLE A Composition of aqueous solutions, amounts are given in parts byweight. Ex 1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8 ¹GLDA — — — — — 68 46 50²MGDA 50 60 70 — 60 — — — ³EDDS — — — 50 — — — — ⁴Citric acid 50 40 3050 — 28 46 50 ⁵Acetic acid — — — — 40 — — ⁶Polyacrylate — — — — — 4 8 —⁷Other 6 7 9 — 7 4 3 3 Water 119 123 126 143 123 113 128 103 ¹GLDA:Dissolvine GL-47-S (Supplier: Akzo Nobel) is a 47% solution of GLDAcontaining 50% water. The amount given in Table A is the amount of GLDA.²MGDA: Trilon (M): (Supplier: BASF) is a 40% solution of MGDA containing55% water. The amount given in Table A is the amount of MGDA. ³EDDS:(analytical grade, Supplier: Sigma Aldrich) is a 35% solution of thetrinatrium salt of EDDS containing about 65% water. The amount given inTable A is the amount of EDDS. ⁴Citric Acid: used as a 50% solution. Theamount given in Table A is the amount citric acid. ⁵Acetic Acid: used asa 50% solution. The amount given in Table A is the amount of aceticacid. ⁶Polyacrylate: Sokalan PA 25 CL (Supplier BASF, supplied asgranules comprising 80% polyacrylate). Average molar mass Mw is 4000.The amount in Table A is the amount of polyacrylate. ⁷Contained inaminopolycarboxylate

The aqueous solutions were heated to boiling in a frying pan. Next,boiling was continued to allow evaporation of water. The liquid waspoured into a fully transparent petri dish and passively allowed to coolto room temperature at which a solid was formed.

The final water levels and the water activity (A_(w)) of the resultingsolid compositions are given in the following table (Table B):

TABLE B Water content (wt. %) Water activity (A_(w)) Example 1 16.5 0.44Example 2 12.8 0.45 Example 3 13.6 0.40 Example 4 13.5 0.50 Example 513.5 0.26 Example 6 8.7 0.32 Example 7 20.8 n.d. Example 8 14.2 n.d.

The solid compositions according to Examples 1 to 8 were subsequentlyanalyzed. First, the translucency was evaluated by eye. All solidcompositions according to the Examples were translucent (eventransparent) and glossy. FIGS. 1 to 3 are photographs taken from thesolid composition of Example 1, 4 and 5 respectively.

X-Ray Diffraction was used to assess the presence of crystals in thesolid compositions. None of the solid compositions of the Examplesshowed detectable crystalline structures and were hence fully amorphouscompositions. FIG. 4 is a WAXS graph of Example 1 (according to theinvention) showing no detectable presence of crystals.

The solids of Example 6 and 7 showed substantially improved plasticitywhen compared to the solid of Example 8

The glass transition temperature (T_(g)) of the solid compositions wasalso analyzed. A relatively high T_(g) and given in the following table(Table C):

TABLE C Glass transition temperature of the solid compositions. Numbersfor each solid composition represent the averages of two independentmeasurements. T_(g) (° C.) Example 1 17 Example 2 23.5 Example 3 33Example 4 2.5 Example 5 18

Examples 9 and 10

Solid amorphous phases according to the invention were made startingfrom an aqueous solution having a formulation as set out in thefollowing Table D.

TABLE D Ex 9 Ex 10 ¹GLDA 80 90 ²Citric acid 20 10 Water 110 111 ¹GLDA:Dissolvine GL-47-S (Supplier: Akzo Nobel) is a 47% solution of GLDA. Theamount given in Table A is the amount of GLDA. ²Citric Acid: used as a50% solution. The amount given in Table A is the amount citric acid.

The solid phases were prepared in the same was as described in Examples1-8. Both solid phases were found to be amorphous and translucent (eventransparent) and glossy.

A 10 wt. % aqueous solution of the first solid phases was prepared andthe pH of these solutions was determined at 25 degrees Celsius. Theresults are shown in Table E.

TABLE E Ex 9 Ex 10 pH (10%) 6.1 9.0

Examples 11 and 12

Solid phases were prepared starting from an aqueous solution having acomposition as set out in the following Table F (amounts are given inparts by weight).

TABLE F Ex 11 Ex 12 ¹GLDA 68 50 ²Citric acid 30 50 ³Polyacrylate 2 —⁴Other 4 3 Water 108 103 ¹GLDA: Dissolvine GL-47-S (Supplier: AkzoNobel) is a 47% solution of GLDA containing 50% water. The amount givenin Table F is the amount of GLDA. ²Citric Acid: used as a 50% solution.The amount given in Table F is the amount citric acid. ³Polyacrylate:Sokalan PA 25 CL (Supplier BASF), supplied as granules comprising 80%polyacrylate. Average molar mass Mw is 4000. The amount in Table F isthe amount of polyacrylate. ⁴Contained in the GLDA

The aqueous solutions were heated to boiling in a frying pan. Nextboiling was continued to allow evaporation of water. The liquid waspoured into a fully transparent petri dish and passively allowed to coolto room temperature at which a solid was formed.

The final water levels and the water activity (A_(w)) of the resultingsolid phases are given in the following table (Table G):

TABLE G Water content (wt. %) Example 11 18.1 Example 12 14.2

The solid phases according to Examples 11 and 12 were subsequentlyanalyzed. First, the translucency was evaluated by eye. Both solidphases were found to be translucent (even transparent) and glossy.

X-Ray Diffraction was used to assess the presence of crystals in thesolid compositions. None of the solid compositions of the Examplesshowed detectable crystalline structures and were hence fully amorphouscompositions.

The solid phase of Example 11 showed substantially improved plasticitywhen compared to the solid phase of Example 12.

Examples 13-15

Solid phases were made starting from an aqueous solution having aformulation as set out in the following Table H (amounts are given inparts by weight). The same ingredients were used as in Examples 11-12.Also the method of manufacture was the same as in Examples 11-12.

TABLE H Ex 13 Ex 14 Ex 15 GLDA 68 47 54 ¹Acetic acid 30 48 42Polyacrylate 2 5 4 Other 4 3 3 Water 108 113 111 ¹Acetic Acid: used as a50% solution. The amount given in Table H is the amount of acetic acid.

The final water levels and the water activity (A_(w)) of the resultingsolid phases are given in the following table (Table I):

TABLE I Water content (wt. %) Example 13 20.2 Example 14 6.1 Example 1515.1

The solid phases according to Examples 13 to 15 were subsequentlyanalyzed. First, the translucency was evaluated by eye. All solid phaseswere translucent (even transparent) and glossy.

X-Ray Diffraction was used to assess the presence of crystals in thesolid phases. None of the solid compositions of the Examples showeddetectable crystalline structures and were hence fully amorphouscompositions.

The solid compositions of Example 13-15 were soft and could easily bedeformed. The composition of Example 14 was less sticky than the othertwo compositions.

Example 16

A solid phase was made starting from an aqueous solution having aformulation as set out in the following Table J (amounts are given inparts by weight). The same ingredients were used as in Examples 11-12.Also the method of manufacture was the same as in Examples 11-12.

TABLE J Parts by weight GLDA 50 Citric acid 50 Polyacrylate 15 Other 3Water 148

X-Ray Diffraction was used to assess the presence of crystals in thesolid material. No crystalline structures were detected. The solidmaterial had a water content of 10 wt. %. The solid material had a glasstransition temperature of 22 degrees Celsius. The glass transitiontemperature can be lowered, for instance, by increasing the watercontent.

1. A shaped detergent product comprising 10 to 100 wt. % of a firstsolid phase and 0 to 90 wt. % of one or more other phases, said firstsolid phase comprising: a) non-crystalline chiral aminopolycarboxylate;b) non-crystalline organic acid other than component a); c) at most 30wt. % water; d) at most 50 wt. % of non-crystalline water-solublecomponent other than component a) or component b); e) at most 20 wt. %of homogeneously dispersed crystalline material; wherein the combinationof the components a), b) and c) is present in the first solid phase in aconcentration of at least 35 wt. % of the total weight of said solidphase; and wherein components a), b) and c) are present in the solidphase in a ratio of from 25 to 88 parts by weight of free acidequivalent of component a): from 10 to 60 parts by weight of free acidequivalent of component b): from 2 to 30 parts by weight of componentc); and wherein the shaped detergent product comprises at least 0.5 wt.% surfactant.
 2. The shaped detergent product according to claim 1,wherein the product contains 10 to 90 wt. % of the first solid phase and10 to 90 wt. % of one or more other solid phases.
 3. The shapeddetergent product according to claim 1, wherein the first solid phase isan amorphous solid phase.
 4. The shaped detergent product according toclaim 1, wherein the first solid phase comprises at least 12 wt. % freeacid equivalent of aminopolycarboxylate selected from glutamic acidN,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA),ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS),iminodimalic acid (IDM) and combinations thereof.
 5. The shapeddetergent product according to claim 1, wherein the first solid phasecontains 5 to 25 wt. % of the component b).
 6. The shaped detergentproduct according to claim 5, wherein the first solid phase comprises 10wt. % free acid equivalent of an acid selected from acetic acid, citricacid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaricacid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharicacids, and combinations thereof.
 7. The shaped detergent productaccording to claim 1, wherein the first solid phase comprises 5 to 25wt. % water.
 8. The shaped detergent product according to claim 1,wherein the first solid phase comprises 12 to 45 wt. % of thewater-soluble component.
 9. The shaped detergent product according toclaim 8, wherein the first solid phase contains 12 to 45 wt. % ofwater-soluble component selected from polycarboxylate polymer,sulfonated polymer and combinations thereof.
 10. The shaped detergentproduct according to claim 1, wherein the combination of components a),b), c) and e) is present in the first solid phase in a combinedconcentration of at least 80 wt. % of the total weight of said solidphase.
 11. The shaped detergent product according to claim 1, wherein atleast part of the shaped detergent product is visually distinct from theremainder of the detergent product parts.
 12. The shaped detergentproduct according to claim 1, wherein the detergent product is aunit-dose detergent product.
 13. A process for the manufacture of theshaped detergent product according claim 1, said process comprising: I.providing an aqueous solution comprising the components a), b) and atleast 35 wt. % water; and II. removing water from the aqueous solutionby evaporation at a temperature of at least 50° C. to produce a liquiddesiccated mixture having a water content of not more than 30 wt. %; andIII. reducing the temperature of the desiccated mixture to less than 25°C. to obtain the shaped detergent product.
 14. The process according toclaim 13, wherein water is removed from the aqueous solution byevaporation at a temperature of at least 95° C.